Basic anthraquinone dye for keratinic fibers and method of making same

ABSTRACT

NEW HAIR DYEING COMPOUND RESPONDING TO THE FORMULA   1-(NH2-(CH2)N-NH-),4-HO-ANTHRAQUINONE   IN WHICH N IS A WHOLE NUMBER LYING BETWEEN 2 AND 6. INCLUSIVE.

United States Patent M Int. Cl: C095 1/50 U.S. Cl. 260-380 1 ClaimABSTRACT OF THE DISCLOSURE New hair dyeing compound responding to theformula NH- 0 H2) ..NH,

(L or! in which n is a whole number lying between 2 and 6 inclusive.

This is a division of application Ser. No. 741,284, filed July 1, 1968now Pat. No. 3,576,587.

The present invention relates to a new chemical compound responding tothe following general formula ll i a) in which n is a whole number lyingbetween 2 and 6 inclusive.

In accordance with the invention the compound of Formult I is obtainedby brominating l-N-acetylaminoalkylamino anthraquinone responding to theformula:

(III) IIIH-(CHz) n NHC O CH:

in which n has the significance hereinbefore indicated, reacting theresulting product with fuming sulfuric acid in the presence of boricacid so as to replace the bromine atom previously attached at position 4with a hydroxy radical, and then hydrolyzing the product in an acidmedium so as to de-acetylate the chain attached at position 1.

It should be noted that the dyes of Formula I yield especially valuableresults when used to dye keratinic fibers, and particularly hair. Thesedyes are, to a substantial extent, soluble in Water, and have aremarkable aflinity for keratinic fiber.

Their use in dyeing compositions makes it possible to obtain veryintense violet shades with a greater resistance to washing than can beobtained with those anthraquinone dyes having an analogous chemicalstructure heretofore known, which have a tertiary amine function at theend of the chain attached to position 1 in Formula I.

The present invention relates to a composition for dyeing keratinicfibers, and in particular hair, which is essentially characterized bythe fact that it comprises, in aqueous solution, at least one dyeresponding to Formula I.

Patented Apr. 23, 1974 In a preferred embodiment of the invention the pHof the dyeing compositions according to the invention lies between 6 and12, and is preferably about 9.

The concentration of the dyes of Formula I in the dyeing compositionsaccording to the invention may vary within broad limits, but ispreferably between 0.01% and 3%.

The dyeing compositions according to the invention may be used attemperatures between 5 and 50 C., but are preferably applied at roomtemperature.

The dyeing compositions according to the invention may also containwetting agents, dispersing agents, penetrating agents, perfumes andlacquers, and any other ingredients conventionally included in hairdyeing compositions. They may also contain other dyes than thoseresponding to Formula I, and particularly anthraquinone, azo, and nitrodyes.

The present invention also relates to a method of dyeing keratinicfibers and particularly human hair, essentially characterized by thefact that the hair is impregnated with an aqueous solution containing atleast one dye responding to the formula I for from 5 to 30 minutes,after which it is shampooed, rinsed and dried.

In order that the invention may be better understood, a method ofpreparing a dye responding to Formula I, and several examplesillustrating the use of said dye on hair, will now be described, purelyby way of illustration.

EXAMPLE 1 Preparation of l-' -aminopropylamino-4-hydroxy anthraquinonemonohydrochloride The preparation may be schematically represented inthe following form:

OBr

(I) IIH-(CHzh-NHCO CH:

O lfH-(CHzh-NH:

First step.Preparation of l-v-acetylaminopropylamino- 4-bromoauthraquinone 0.3 mole (9.66 g.) of l-y-acetylaminopropylaminoanthraquinone is dissolved in cc. of acetic acid at 50 C. 0.03 mole (2.4g.) of sodium acetate is added, followed by 0.03 mole (4.8 g.) ofbromine, which is added little by little, while stirring. The reactionmixture is kept at 50 C. for 7 hours, and then at 20 C. for 15 hours,and then poured into water. The crude product is dried Calculated forAnalysis CmHnNzOsBI Found percent. 56. 86 56. 79-56. 89 percent- 4. 244. 43-4. 43 N, percent..- 6. 98 7. -6. 96 Br, percent"--. 19. 95 19.54-19. 32

Second step.--Preparation of l-y-acetylaminopropylamino-4-hydroxyanthraquinone 0.0238 mole (9.5 g.) of 1- -acetylaminopropylamino-4-bromo anthraquinone is heated for 4 hours at 120 C. in the presence of95 g. of 10% fuming sulfuric acid and 4.75 g. of boric acid. Aftercooling, the reaction mixture is poured over cracked ice and neutralizedwith a sodium hydroxide solution. 10 cc. of acetic anhydride is addedand the mixture heated for 30 minutes at 70 C. After cooling, drying andWashing with water yields 7.7 g. of 1-'y-acetylaminopropylamino 4hydroxy anthraquinone which, after recrystallization in chlorobenzene,melts at 198 C.

Analysis of this product yields the following results:

Calculated for Analysis CmEh NaOi Found C percent 67. 46 67. 59-67. 53H, percent- 5. 32 5. 49- 5. 41 N, percent.-." 8. 28 8. 8. 10

Third step.--Preparation of 1w-aminopropylamino-4-hydroxy anthraquinonemonohydrochloride 4 EXAMPLE 2 The following dyeing composition isprepared: 1-'y-aminopropylamino-4-hydroxy anthraquinonemono-hydrochloride 0.33 g. Lauric alcohol with 10.5 moles of ethyleneoxide 2 g. 2N solution of Na CO q.s.p pH=7 Water, q.s.p 100 g.

This composition is applied to bright golden chestnut hair, and left toact for 10 minutes, after which the hair is shampooed and rinsed. Avioline chestnut is obtained.

EXAMPLE 3 The following dyeing composition is prepared: 1-'-aminopropylamino-4-hydroxy anthraquinone This composition is applied towhite hair, and left to act for 15 minutes, the hair is then shampooedand rinsed. A bright burnt chestnut is obtained.

What is claimed is:

1. New anthraquinone dye responding to the formula:

ol NH- CHm-NH,

in which n is a whole number lying between 2 and 6 inclusive.

References Cited UNITED STATES PATENTS 3/ 1964 Turetzky et al 260-2475OTHER REFERENCES Houben, Das Anthracen und die Anthrachinone, pp.308-10, 472 (1929).

LORRAINE A. WEINBERGER, Primary Examiner R. GERSTL, Assistant Examiner

